2, 6-dioxaspiro (3, 3)heptane treated cellulose fabric and the production thereof



3,624 080 2,6 -DIUXASPIRQ(3,3)HEPTANE TREATED CEL- LULOiiE FABRIC ANDTHE PRODUCTKQN THEREGF Peter L. De Benneville, Philadelphia, Pa, andRichard 0. Steele, Moerestown, N.J., assignors to Rohm & Haas Company,Philadelphia, Pa, a corporation of Delaware No Drawing. Filed Oct. 14,1957, Ser. No. 689,788 20 Claims. (Cl. 8-120) reduced shrinkage onWashing so that partial or complete dimensional stabilization may beeifected. The invention also embraces the treated fabrics obtained.

In accordance with the present invention, it has been found thatcellulosic fabrics, woven, knitted, or other-,

wise formed, have reduced shrinkage on washing and acquire resistance tocreasing and crushing when they are treated with2,6-dioxaspiro(3,3)heptane of the formula C C H2 H:

For convenience, this compound will be hereinafter referred to by theshorter term dioxaspiroheptane. The extent of modification by means ofthis compound may be controlled by variation in the proportion of thedioxaspiroheptane and by variation in the amount of catalyst. employedduring the treatment therewith.

The treatment with dioxaspiroheptane may be effected most advantageouslyby means of aqueous solutions thereof in which the dioxaspiroheptane isdissolved at a concentration which may vary from 1 to 30% by weight.Preferably, the concentration is from 5 to 15% to obtain the maximumbenefits in crease-proofing and the like.

The treatment with dioxaspiroheptane may be carried out in the presenceof a catalyst. We have found that the most effective catalysts are metalsalts of acids having the composition H,(XYb), Where H is hydrogen, a isan integer which depends on the valence of the complex ion and may havea value of 1 to'3, X is a non-metal selected from the group consistingof boron, silicon, sulfur, and chlorine, said non-metal being in a statewhere its valence is from 3 to 7, Y is fluorine or oxygen, and b is aninteger having a value of 4 or 6. The metals of these salts are those ofgroups lb, II, 1111), IV, and VIII of the periodic table in T. Moeller,Inorganic Chemistry, John Wiley 8: Sons, New York, 1952, which have anatomic weight of at least 12. Salts of perchloric and fluoboric acidsare very efiicient catalysts, particularly their zinc, lead, copper, andmagnesium compounds. Salts of sulfuric acid, such as aluminum and coppersulfate, and of fiuosilicic acid, such as magnesium, zinc, and copperfluosilicates, also are active as catalysts. Other acidic compounds,oxalic acid, for example, may also be used as catalysts.

Conveniently, the amount of catalyst may vary from about 0.2 to 2% andis preferably in the range of 0.5 to 1% concentration in the aqueoussolution of dioxaspiroheptane.

The catalyzed solution of dioxaspiroheptane is compatible with solutionsor dispersions of most of the common textile finishing agents, such assynthetic polymer latices and aminoplast resins or precondensates, sothat they may be applied with the dioxaspiroheptane to produce changesin the hand or other properties of the fabric.

The aqueous solution containing dioxaspiroheptane and aszaass PatentedMar. 6, 1962 catalyst may be applied to the fabric in any suitablemanner such as by spraying or impregnation. In general, it is preferableto use some method of impregnation. With .piece goods, this isconveniently carried out with the various machines used for treatingfabric in open width, such as pads or jigs. However, it is not requiredthat the impregnation be carried out in open width, and the fabric maybe handled in any form. In treating garments or other articles made fromcellulosic fabrics, the impregnation may be carried out in a tumblewheel, laundry machne, or other suitable equipment. After application ofthe solution, it is desirable to remove the excess solution by squeezingthe fabric between rollers, or by shaking or centrifuging it, in orderto insure a more even treatment. The fabric treated with solution may bedried, such as by air-drying at normal room temperature or by heating ina drying oven at temperatures of F. and up. The drying and curingoperations are preferably done with the fabric open and flat, so that itwill have a smooth and even appearance when finished. In a preferredembodiment, the impregnated fabric, immediately after impregnation andwithout preliminary low-temperature drying is carried in open width by atenter frame through a curing oven where it is subjected to temperaturesof about 250 F. to about 400 F. or higher for a period of time rangingfrom about one minute to about one-half hour or more, the shorter periodbeing employed at the higher temperature and vice versa. Entirelysatisfactory results are obtained by heating for ten minutes at about300 F. This curing operation not only dries the impregnated fabric butapparently causes a reaction between the dioxaspiroheptane and thehydroxyl groups of the cellulose. Presumably, the hydroxyl group of acellulose molecule causes an opening of the oxide ring and addition toform some such linkage as may be represented by the following formula:

noon: CHZOH where Cel represents a cellulose molecule. The two oxiderings in the dioxaspiroheptane may react with hydroxyl groups on thesame cellulose molecule, or on different molecules. It is not intended,however, that the present invention be limited to this theory ofoperation.

The treated fabrics exhibit a high degree of crush resistance and creaserecovery with little or no change in the hand or feel of the fabric. Thetreatment does not discolor the fabric. In addition, the treated fabricshave the important advantage that they do not retain chlorine, so thatthe use of bleaching agents containing chlorine does not causedeterioration either by way of discoloration or loss in tensile strengtheven when the treated fabrics which have been bleanched are subjected toironing temperatures. The treated fabrics are also resistant toshrinkage during laundering, and the treatment is very permanent towardslaundering, dry-cleaning, and other procedures for cleaning textilefabrics.

' The following examples illustrate the present invention, and the partsand percentages therein are byweight unless otherwise noted. The creaserecovery values given below were determined by the Shirley Instituteprocedure (British Standards Handbook No. 11, 1949 ed., page 128).

EXAMPLE 1 A sample of cotton printcloth was saturated with an aqueoussolution containing 20% dioxaspiroheptane and 1% zinc perchlorate. Itwas then put into an oven at C. and baked for 15 minutes. Controlstreated with water and 1% zinc perchlorate were similarly prepared.

After being conditioned the samples had the following crease recoveryvalues:

The dioxaspiroheptane-treated fabric was insoluble in cuprammoniumhydroxide while the controls dissolved readily.

The durability of the treatment was shown by the following tests.Samples of the dioxaspiroheptane-treated fabric were extracted (1) inboiling water for one hour, (2) in 0.1 N HCl at 80 C. for one hour, and(3) in 0.1 NaOH for 24 hours at 20 C. The extracted samples were stillinsoluble in cuprammonium hydroxide, and had good crease recovery,v asshown by the following data:

Degrees Water extraction 132 HCl extraction- 125 NaOH extraction 123EXAMPLE 2 EXAMPLE 3 Samples of cotton printcloth were saturated with 20%aqueous solutions of dioxaspiroheptane containing various amounts ofzinc perchlorate catalyst. They were then cured in an oven at 150 C. for15 minutes. After being conditioned, the samples were tested for creaserecovery. The following results were obtained:

Table A Concentration Crease of Zn(OlOi)a recovery (percent) (degrees)EXAMPLE 4 Samples of cotton printcloth were treated with aqueoussolutions of dioxaspiroheptane at various concentrations, each solutioncontaining either 0.5% or 1.0% of Zinc perchlorate as catalyst and thenbaked at 150 C. for 15 minutes. Water and catalyst controls were alsoprepared. The samples were conditioned and tested for crease recoverywith the following results:

Table B Crease recovery (degrees) Concentration of dioxaspiroheptane(percent) 0.5% catalyst 1.0% catalyst EXAMPLE 5 Various types of cottonfabrics were treated by saturation in an aqueous solution containingdioxaspiroheptame and 0.75% of zinc perchlorate. After heating in anoven for 15 minutes at 150 C., the results summarized in the followingtable were obtained:

Table C Grease recovery angles Fabric Count Water Treated Printcloth x80 80 125 Broadeloth 120 x 60 123 Muslin 54 x 46 78 99 Lawn 107 X 97 08128 EXAMPLE 6 A sample of cotton printcloth was impregnated with asolution containing 20% dioxaspiroheptane and 0.75% zinc perchlorateunder conditions such that the wet pickup of the fabric was about of itsdry weight. The sample was held on a pin-frame at its orginal dimensionsand baked for 15 minutes in an oven at 150 C. A watertreated control wasalso prepared. The two samples were then washed by the procedure givenin Method 5550 of the Federal Specification CCC-T-191b. The areashrinkage of the control was 19.7% while that of the treated sample wasonly 4.6%.

Samples of the treated fabric taken before and after washing werechlorinated in 50 times their weight of a bleach bath containing 0.25%of available chlorine for 15 minutes at room temperature. After beingdried, and conditioned, the samples were pressed under an iron at 365 C.for 0.5 minute. Neither sample showed any discoloration or loss oftensile strength after this procedure.

EXAMPLE 7 Table D Crease recovery (degrees) Time of baking (minutes) 275F. 300 F. 325 F.

EXAMPLE 8 A sample of cotton printcloth was treated with a solutioncontaining 10% of dioxaspiroheptane, 1% of zinc perchlorate, and 4% of apartially condensed urea-formaldehyde resin. The treated fabric wascured for 15 minutes at C. After being conditioned, it had a stiffer,firmer, more resilient hand, and a crease recovery of 137.

EXAMPLE 9 A sample of cotton printcloth was treated with a solutioncontaining a mixture of 5% dioxaspiroheptane and 5%dimethylol-N,N-ethyleneurea with 1% zinc fluoborate as a catalyst. Theapplication was made on a textile pad and the impregnated fabric wasbaked for 1 0 minutes at 150 C. After the fabric was conditioned, itscrease recovery angle was 139.

We claim:

1. The process comprising impregnating a cellulose fabric With anaqueous solution of 2,6-dioxaspiro(3,3)- heptane and a catalyst, andheating the impregnated fabric at a temperature of about 250 to 400 F.,until the crease resistance of the fabric is increased.

2. A process as defined in claim 1 in which the fabric is cotton.

3. A process as defined in claim 1 in which the fabric is regeneratedcellulose rayon.

4. The process comprising impregnating a cellulose fabric With anaqueous solution containing 1 to 30% by weight of2,6-dioxaspiro(3,3)heptans and 0.2 to 2% of a catalyst and heating theimpregnated fabric at a temperature of about 250 to 400 F. until thecrease-resistance of the fabric is increased.

5. A process as defined in claim 4 in which the fabric is cotton.

6. A process as defined in claim 4 in which the fabric is regeneratedcellulose rayon.

7. The process comprising impregnating a cellulose fabric with anaqueous solution containing 1 to 30% by weight of2,6-dioxaspiro(3,3)heptane and, as a catalyst, 0.2 to 2% of a memberselected from the group consisting of aluminum and copper sulfates,oxalic acid, and metal salts of an acid of the formula H (XY where H ishydrogen, a is an integer having a value of 1 to 3, X is a memberselected from the group consisting of boron, silicon, sulfur, andchlorine, Y is a member selected from the group consisting of fluorineand oxygen, and b is an integer selected from 4 and 6, said metal havingan atomic weight of at least 12 and being selected from the groupconsisting of those in groups 1b, II, IIIb, IV, and VIII of the periodictable, and heating the impregnated fabric at a temperature of about 250to 400 F. until the crease-resistance of the fabric is increased.

8. A process according to claim 7 in which the fabric is cotton.

9. A process according to claim 7 in which the fabric is regeneratedcellulose rayon.

10. The process comprising impregnating a cellulose fabric with anaqueous solution containing 1 to 30% by weight of2,6-dioxaspiro(3,3)heptane and 0.2 to 2% of magnesium fiuoborate, andheating the impregnated fabric 6 at a temperature of about 250 to 400 F.until the crease-resistance of the fabric is increased.

11. A process as defined in claim 10 in which the fabric is cotton.

12. A process as defined in claim 10 in which the fabric is regeneratedcellulose rayon.

13. The process comprising impregnating a cellulose fabric with anaqueous solution containing 1 to 30% by Weight of2,6-dioxaspiro(3,3)heptane and 0.2 to 2% of zinc perchlorate and heatingthe impregnated fabric at a temperature of about 250 to 400 F. until thecreaseresistance of the fabric is increased.

14. A process as defined in claim 13 in which the fabric is cotton.

15. A process as defined in claim 13 in which the fabric is regeneratedcellulose rayon.

16. The process comprising impregnating a cellulose fabric with anaqueous solution containing 1 to 30% by weight of2,6-dioxaspiro(3,3)heptane and 0.2 to 2% of zinc fiuoborate and heatingthe impregnated fabric at a temperature of about 250 to 400 F. until thecreaseresistance of the fabric is increased.

17. A process as defined in claim 16 in which the fabric is cotton.

18. A cellulose fabric having improved crease resistance obtained by theprocess of claim 1.

19. A cotton fabric having improved crease resistance obtained by theprocess of claim 5.

20. A regenerated cellulose fabric having improved crease resistanceobtained by the process of claim 6.

References Cited in the file of this patent UNITED STATES PATENTS2,752,269 Condo June 26, 1956 2,764,575 Kohler Sept. 25, 1956 2,774,691Schroeder Dec. 18, 1956 2,794,754 Schroeder June 4, 1957

1. THE PROCESS COMPRISING IMPREGNATING A CELLULOSE FABRIC WITH ANAQUEOUS SOLUTION OF 2,6-DIOXASPIRO (3,3)HEPTANE AND A CATALYST, ANDHEATING THE IMPREGNATED FABRIC AT A TEMPERATURE OF ABOUT 250* TO 400*F.,UNTIL THE CREASE RESISTANCE OF THE FABRIC IS INCREASED.